TWI817024B - Chemical mechanical polishing slurry composition for mult film polishing and polishing method using the same - Google Patents

Abstract

The present invention relates to a chemical mechanical polishing slurry composition for polishing multi-layer films and a polishing method using the same. According to an embodiment of the present invention, the chemical mechanical polishing slurry composition for polishing multi-layer films includes: polishing particles; Surface roughness improvers, including water-soluble polymers; polish conditioners, including organic acids; and polish profile improvers, including nonionic surfactants.

Description

Chemical mechanical polishing (CMP) slurry composition for polishing multilayer films and polishing method using same

The present invention relates to a chemical mechanical polishing (CMP) slurry composition for polishing multi-layer films and a polishing method using the same.

In the semiconductor manufacturing process, Chemical Mechanical Planarization (CMP) is used in the surface polishing process to form multi-layer devices with high integration density, and as the pattern size of semiconductors gradually decreases, the pattern used to manufacture the pattern The importance of the polishing process has also become increasingly apparent.

In the process of manufacturing semiconductor devices, single crystal silicon wafers are used as the main material, which can prepare initial materials at low cost and prepare oxide films with excellent electrical insulation properties. Since the surface roughness of the silicon wafer has a great impact on subsequent processes in the semiconductor manufacturing process, it is essential to use the chemical mechanical polishing process for planarization.

Currently, polycrystalline silicon films are used in the preparation process of integrated circuits (ICs), recess channel array transistors (RCAT) and three-dimensional fin field effect transistors (FinFET). Moreover, it is necessary to study how to use chemical machinery Polishing process to minimize surface roughness.

Specifically, polycrystalline silicon is obtained by crystallizing amorphous silicon. However, the widely used laser crystallization method has the disadvantage of worsening the surface roughness of the polycrystalline silicon film, so it is necessary to improve the surface roughness thereof.

In addition, the chemical mechanical polishing slurry composition is used for polishing silicon materials, that is, single crystal silicon, amorphous silicon, polycrystalline silicon and other elemental silicon, as well as silicon nitride, silicon oxide and other silicon compounds. It is used to polish silicon substrates such as single crystal silicon substrates, or to polish elemental silicon films such as amorphous silicon films or polycrystalline silicon films formed on silicon substrates, or to polish films of silicon compounds such as silicon nitride films and silicon oxide films.

Generally speaking, chemical mechanical polishing slurry compositions can be divided into various types according to the type and characteristics of the polishing object, but recently there is a need to develop chemical mechanical polishing slurry combinations that can simultaneously polish silicon films, silicon nitride films, silicon oxide films, etc. things.

For this reason, research and development of chemical mechanical polishing slurry compositions that can improve the polishing selectivity and polishing speed are being actively carried out. However, there is little research today on multifunctional slurry compositions that can simultaneously improve surface roughness, defects, or scratches when applied to different types of membrane qualities.

Problems to be solved by the invention:

The purpose of the present invention is to solve the above problems, that is, to provide a chemical mechanical polishing (CMP) composition for polishing multi-layer films and a polishing method using the same, which can improve the surface roughness of the polycrystalline silicon film while also improving the polycrystalline silicon. Film and silicon nitride film defects (Defect).

However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned can be clearly understood by those of ordinary skill in the art from the following description.

Technical means to solve the problem:

According to one aspect of the present invention, a chemical mechanical polishing slurry composition for polishing multi-layer films is provided, including: polishing particles; a surface roughness improver, including a water-soluble polymer; and a polishing conditioner, including an organic acid. ; and polish profile improvers, including nonionic surfactants.

According to an embodiment, the chemical mechanical polishing slurry composition for polishing multi-layer films further includes a defect improver, and the defect improver includes an anionic surfactant.

According to an embodiment, the anionic surfactant may include polyacrylic acid, polymethacrylic acid, polystyrene-acrylic acid copolymer, acrylic acid-maleic acid copolymer, acrylic acid-ethylene copolymer, acrylic acid-acrylamide At least any one of the group consisting of amine copolymers and acrylic acid-polyacrylamide copolymers.

According to an embodiment, the defect improving agent may account for 0.005 to 0.1 weight percent in the chemical mechanical polishing slurry composition for polishing.

According to an embodiment, the polishing particles may include at least any one selected from the group consisting of metal oxides, metal oxides coated with organic or inorganic substances, and the metal oxide in a colloidal state, the metal The oxide may include at least any one selected from the group consisting of silicon dioxide, ceria, zirconium oxide, aluminum oxide, titanium dioxide, barium titanium dioxide, germanium oxide, manganese oxide, and magnesium oxide.

According to an embodiment, the polishing particles can be prepared by a liquid phase method and dispersed so that the surface of the polishing particles has a negative charge.

According to an embodiment, the particle size of the polishing particles may be 10 nanometers to 200 nanometers.

According to an embodiment, the polishing particles may account for 0.1 to 10 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films.

According to an embodiment, the weight average molecular weight of the water-soluble polymer may be 10,000 to 1,000,000.

According to an embodiment, the water-soluble polymer may include hydroxyethyl cellulose (HEC), hydroxymethyl cellulose (HMC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), carboxymethylcellulose (CMC), methylcellulose (MC), methylhydroxyethylcellulose (MHEC), chitosan, gelatin, xanthan gum, collagen, carrageenan, halothane , at least any one of the group consisting of pectin, chondroitin sulfate, alginic acid, dextran, β-glucan and hyaluronic acid.

According to an embodiment, the surface roughness improver may account for 0.0005 to 0.5 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films.

According to an embodiment, the organic acid may include succinic acid, malic acid, malonic acid, adipic acid, tartaric acid, Glutaric acid, glycollic acid, aspartic acid, itaconic acid, tricarballylic acid, pimelic acid, caprylic acid Suberic acid, sebacic acid, stearic acid, pyruvic acid, acetoacetic acid, glyoxylic acid, azelaic acid ( azelaic acid), fumaric acid, glutaconic acid, traumatic acid, muconic acid, aconic acid, carballylic acid, triglyceride Tribasic acid, mellitic acid, isocitric acid, citric acid, lactic acid, gluconic acid, maleic acid , ascorbic acid, iminoacetic acid, oxalic acid, pyrogallic acid, formic acid, acetic acid, propionic acid , butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, ten In the group consisting of undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecanoic acid and palmitic acid At least any of them.

According to an embodiment, the polishing conditioner may account for 0.01 to 1 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films.

According to one embodiment, the chemical mechanical polishing slurry composition for polishing multi-layer films further includes a pH adjuster. The pH adjuster may include triethanolamine, trimethanolamine, monoethanolamine, diethanolamine, diethanolamine, or triethanolamine. Methylbenzylamine, ethoxybenzylamine, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, tris(hydroxymethyl)aminomethane, 2 -Amino-1-butanol, 2-amino-2-methyl-1,3-propanediol, dimethylaminomethylpropanol, diethylaminoethanol, monoisopropanolamine, aminoethylethanolamine, 3- Amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 1-amino-pentanol, 2-(2-aminoethylamino)ethanol, 2-dimethylamino -At least one of the group consisting of 2-methyl-1-propanol and N,N-diethylethanolamine.

According to an embodiment, the nonionic surfactant may include polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene-propylene copolymer (polyethylene-propylene copolymer), polyalkyl oxide At least any one of the group consisting of (polyalkyl oxide), polyoxyethylene (POE), polyethylene oxide (polyethylene oxide) and polypropylene oxide (polypropylene oxide).

According to an embodiment, the polishing profile improver may account for 0.01 to 1 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films.

According to an embodiment, the pH range of the chemical mechanical polishing slurry composition for polishing multi-layer films may be from 3 to 7.

According to an embodiment, the multilayer film may include a polycrystalline silicon film, a silicon nitride film, or a combination of both.

Effects of the invention:

The chemical mechanical polishing (CMP) composition for polishing a multilayer film according to the present invention can improve the surface roughness of a polycrystalline silicon film, a silicon nitride film, or a combination of both by including a surface roughness improver including a water-soluble polymer. Surface roughness after polishing of multilayer films.

In addition, by including a defect improving agent including a nonionic surfactant, occurrence of defects after polishing a multilayer film including a polycrystalline silicon film, a silicon nitride film, or a combination of both can be improved.

Hereinafter, embodiments of the present invention will be described in detail. Various modifications can be made to the following embodiments. The patentable scope of this application is not limited or limited by the following embodiments, and all changes to all embodiments, their equivalents and even their substitutes are included in the patentable scope.

The terms used in the embodiments are only used to describe specific embodiments and are not used to limit the embodiments. Unless otherwise specified in the content, singular expressions include the plural. In this specification, terms such as "including" or "having" are used to express the presence of the features, numbers, steps, operations, components, accessories or combinations thereof described in the specification, and do not exclude the presence of one or more other features. , numbers, steps, operations, components, accessories or combinations thereof, or additional functions.

Unless otherwise defined, all terms including technical or scientific terms used herein have the usual meaning as commonly understood by one of ordinary skill in the art. Commonly used terms that have the same definitions in dictionaries should be understood to have meanings that are consistent with the usual content of the relevant technology. Unless explicitly stated in this application, they cannot be overly idealized or interpreted as having formal meanings.

In describing the present invention, when it is judged that detailed description of related conventional functions or structures unnecessarily obscures the gist of the present invention, detailed description thereof will be omitted.

Hereinafter, the chemical mechanical polishing (CMP) composition for polishing multilayer films of the present invention and the polishing method using the same will be specifically described with reference to examples. However, the present invention is not limited to the above-described embodiment.

According to one aspect of the present invention, a chemical mechanical polishing slurry composition for polishing multi-layer films is provided, including: polishing particles; a surface roughness improver, including a water-soluble polymer; and a polishing conditioner, including an organic acid. ; and polish profile improvers, including nonionic surfactants.

The chemical mechanical polishing slurry composition for polishing multilayer films of the present invention can improve the removal rate of surface hillocks generated when polycrystalline silicon is grown and can improve the surface roughness improver containing a water-soluble polymer. The polished surface roughness of the polishing film.

According to an embodiment, the chemical mechanical polishing slurry composition for polishing multi-layer films further includes a defect improver, and the defect improver includes an anionic surfactant.

According to an embodiment, the anionic surfactant may comprise polyacrylic acid, polymethacrylic acid, polystyrene-acrylic acid copolymer, acrylic acid-maleic acid copolymer, acrylic acid-ethylene copolymer, acrylic acid-acrylamide copolymer At least any one of the group consisting of acrylic acid-polyacrylamide copolymer.

According to an embodiment, the weight average molecular weight of the anionic surfactant may be 1,000 to 30,000.

Preferably, the weight average molecular weight of the anionic surfactant can be 1,000 to 25,000, more preferably, it can be 1,500 to 25,000, still more preferably, it can be 1,500 to 20,000.

When the weight average molecular weight of the anionic surfactant is less than 1,000, the defect improvement rate may be reduced; when it exceeds 30,000, the polishing speed may be reduced.

According to an embodiment, the defect improving agent may account for 0.005 to 0.1 weight percent in the chemical mechanical polishing slurry composition for polishing.

When the defect improver accounts for less than 0.01 weight percent in the chemical mechanical polishing composition for polishing multi-layer films, the defect improvement rate may be reduced; when it exceeds 0.1 weight percent, flocculation and aggregation may occur or the dispersion stability may be reduced. properties, thereby reducing the defect improvement rate.

According to an embodiment, the polishing particles may include at least any one selected from the group consisting of metal oxides, metal oxides coated with organic or inorganic substances, and the metal oxide in a colloidal state, the metal The oxide may include at least any one selected from the group consisting of silicon dioxide, ceria, zirconium oxide, aluminum oxide, titanium dioxide, barium titanium dioxide, germanium oxide, manganese oxide, and magnesium oxide.

According to an embodiment, the surface of the polishing particles can be modified from OH to COO-. Through the above surface modification, the polishing particles can have a strong negative charge in all pH ranges. Due to the strong repulsive force between the surface-modified polishing particles and the polycrystalline silicon film, the adsorption of the polished polycrystalline silicon film-like polishing particles can be minimized.

According to an embodiment, the polishing particles can be prepared by a liquid phase method and dispersed so that the surface of the polishing particles has a negative charge.

The polishing particles may include polishing particles prepared by a liquid phase method, but are not limited thereto. The liquid phase method can be achieved by applying the sol-gel method (making the polishing particle precursor chemically react in an aqueous solution and growing crystals to obtain microparticles) or the co-precipitation method (making the polishing particle ions precipitate in the aqueous solution) and It is prepared by hydrothermal synthesis (forming polishing particles under high temperature and high pressure), etc. The polishing particles prepared by the liquid phase method are dispersed so that the surface of the polishing particles has a negative charge.

According to an embodiment, the particle size of the polishing particles may be 10 nanometers (nm) to 200 nanometers.

Preferably, the particle size of the polishing particles can be from 10 nanometers to 150 nanometers, more preferably, from 30 nanometers to 150 nanometers, still more preferably, from 30 nanometers to 100 nanometers. .

The measurement of the average particle size of the polishing particles is the average of the particle sizes of multiple particles within the visible range that can be measured by scanning electron microscopy analysis or dynamic light scattering. When the size of the polishing particles is less than 10 nanometers, it will reduce the polishing rate of the polishing particles, making it difficult to achieve the required selectivity; when it exceeds 200 nanometers, excessive polishing will occur, making it difficult to control the selection. ratio, and may cause dents, corrosion and surface defects.

According to an embodiment, in addition to single-size particles, the polishing particles may use mixed particles containing a multi-dispersion particle distribution. For example, the polishing particles may be mixed with two different average particle sizes to have double particle sizes. Particle distribution in the form of a peak (bimodal); or it can be a particle distribution with three peaks by mixing polishing particles with three different average particle sizes. Alternatively, it may be possible to have a polydisperse particle distribution by mixing more than four polishing particles with different average particle sizes. By mixing larger polishing particles with relatively smaller polishing particles, better dispersion can be achieved and scratches on the wafer surface can be reduced.

According to an embodiment, the shape of the polishing particles may include at least any one selected from the group consisting of spherical, rectangular, needle-shaped, and plate-shaped. Preferably, the shape may be spherical.

According to an embodiment, the polishing particles may be single crystals. When using single crystal polishing particles, compared with polycrystalline polishing particles, the effect of reducing scratches can be achieved, and the dent phenomenon and post-polishing cleanliness can be improved.

According to an embodiment, the polishing particles may account for 0.1 to 10 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films.

When the polishing particles account for less than 1 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films, the polishing speed may be reduced; when it exceeds 10 weight percent, the polishing speed and the number of polishing particles may be excessively increased. is increased, so the adsorption of polishing particles remaining on the surface may lead to surface defects.

According to an embodiment, the weight average molecular weight of the water-soluble polymer may be 10,000 to 1,000,000.

When the weight average molecular weight of the water-soluble polymer is less than 10,000, it may be difficult to remove the hillocks on the polycrystalline silicon film; when it exceeds 1,000,000, not only the hillocks may be excessively removed, but the polished film may also be lost.

According to one embodiment, in order to remove the hillocks on the polycrystalline silicon film, a laminar flow is formed between the polycrystalline silicon wafer and the pad through the slurry composition during the polishing process. When the slurry composition fails to form a laminar flow between the polycrystalline silicon wafer and the pad and is thus in a turbulent flow state, the mechanical polishing becomes irregular and the surface becomes rough. In order to form laminar flow, it is best to add water-soluble polymers with longer molecular chains.

According to an embodiment, the water-soluble polymer may include hydroxyethyl cellulose (HEC), hydroxymethyl cellulose (HMC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), carboxymethylcellulose (CMC), methylcellulose (MC), methylhydroxyethylcellulose (MHEC), chitosan, gelatin, xanthan gum, collagen, carrageenan, halothane , at least any one of the group consisting of pectin, chondroitin sulfate, alginic acid, dextran, β-glucan and hyaluronic acid.

According to an embodiment, in the water-soluble polymer, the water-soluble polymer cellulose can be cellulose obtained from photosynthesis of plants, and can be prepared by hydrolyzing lignocellulose regardless of the presence or absence of lignin. And use, and can use, industrially prepared and sold water-soluble polymer cellulose.

According to an embodiment, the surface roughness improver may account for 0.0005 to 0.5 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films.

When the surface roughness improver accounts for less than 0.0005 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films, it may not be easy to remove the hillocks on the polycrystalline silicon film; when it exceeds 0.5 weight percent, not only may excessive By removing the hillocks, you may also lose the polished film.

According to an embodiment, the organic acid may include succinic acid, malic acid, malonic acid, adipic acid, tartaric acid, Glutaric acid, glycollic acid, aspartic acid, itaconic acid, tricarballylic acid, pimelic acid, caprylic acid Suberic acid, sebacic acid, stearic acid, pyruvic acid, acetoacetic acid, glyoxylic acid, azelaic acid ( azelaic acid), fumaric acid, glutaconic acid, traumatic acid, muconic acid, aconic acid, carballylic acid, triglyceride Tribasic acid, mellitic acid, isocitric acid, citric acid, lactic acid, gluconic acid, maleic acid , ascorbic acid, iminoacetic acid, oxalic acid, pyrogallic acid, formic acid, acetic acid, propionic acid , butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, ten In the group consisting of undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecanoic acid and palmitic acid At least any of them.

According to an embodiment, the polishing conditioner may account for 0.01 to 1 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films.

When the polishing conditioner accounts for less than 0.01 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films, the polishing speed may be reduced; when it exceeds 1 weight percent, the polished film may be over-polished.

According to one embodiment, the chemical mechanical polishing slurry composition for polishing multi-layer films further includes a pH adjuster. The pH adjuster may include triethanolamine, trimethanolamine, monoethanolamine, diethanolamine, diethanolamine, or triethanolamine. Methylbenzylamine, ethoxybenzylamine, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, tris(hydroxymethyl)aminomethane, 2 -Amino-1-butanol, 2-amino-2-methyl-1,3-propanediol, dimethylaminomethylpropanol, diethylaminoethanol, monoisopropanolamine, aminoethylethanolamine, 3- Amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 1-amino-pentanol, 2-(2-aminoethylamino)ethanol, 2-dimethylamino -At least one of the group consisting of 2-methyl-1-propanol and N,N-diethylethanolamine.

According to an embodiment, the pH adjuster may account for 0.01 to 1 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films.

When the pH adjuster accounts for less than 0.01 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films, the polishing speed may be reduced; when it exceeds 1 weight percent, the polished film may be over-polished.

According to an embodiment, the nonionic surfactant may include polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene-propylene copolymer (polyethylene-propylene copolymer), polyalkyl oxide At least any one of the group consisting of (polyalkyl oxide), polyoxyethylene (POE), polyethylene oxide (polyethylene oxide) and polypropylene oxide (polypropylene oxide).

According to an embodiment, the weight average molecular weight of the nonionic surfactant may be 100 to 1000.

According to an embodiment, the polishing profile improver may account for 0.01 to 1 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films.

When the polishing profile improver accounts for less than 0.01 weight percent in the chemical mechanical polishing composition for polishing multi-layer films, over-polishing may occur; when it exceeds 0.1 weight percent, the dispersion stability of the composition will be reduced. Micro scratches may therefore occur.

According to an embodiment, the pH range of the chemical mechanical polishing slurry composition for polishing multi-layer films may be from 3 to 7.

When the pH range is less than 3 or exceeds 7, the defect improvement rate may be reduced.

According to an embodiment, the multilayer film may include a polycrystalline silicon film, a silicon nitride film, or a combination of both.

According to another aspect of the present invention, a polishing method is provided, including the step of polishing a semiconductor wafer including a multilayer film by using the chemical mechanical polishing slurry composition for polishing a multilayer film.

Hereinafter, the present invention will be described in detail with reference to the following Examples and Comparative Examples. However, the following Examples and Comparative Examples are only cited for the purpose of illustration, and the technical idea of the present invention is not limited thereto.

[Example 1]:

Add 1 weight percent of surface-modified colloidal silica polishing particles (PL-3D) with a particle size of 80 nanometers, 0.08 weight percent of succinic acid as carboxylic acid, and 0.03 weight percent of succinic acid as surface roughness. The weight average molecular weight of the improver is hydroxyethyl cellulose (HEC) of 90,000, 0.05 weight percent of polyethylene glycol (PEG) with a weight average molecular weight of 600 as a polishing profile improver, and 0.025 weight percent of a defect improver. Polyacrylic acid (PAA 1X) with a weight average molecular weight of 2000 was mixed with triethanolamine as a pH adjuster to prepare a chemical mechanical polishing slurry composition with a pH value of 3.5 for polishing multi-layer films.

By using this chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed for 60 seconds under the evaluation conditions of a pressure of 2 psi, a carrier RPM of 78/83, and a flow rate of 250 ml/min.

[Example 2]:

In Example 1, a chemical mechanical polishing slurry composition for polishing multilayer films was prepared in the same manner as Example 1, except that 0.005 weight percent of polyacrylic acid (PAA 1X) as a defect improver was added.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Example 3]:

In Example 1, chemical mechanical polishing for polishing multilayer films was prepared in the same manner as in Example 1, except that 0.005 weight percent of polyacrylic acid (PAA 5X) with a weight average molecular weight of 10,000 as a defect improver was added. Slurry composition.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Example 4]:

In Example 1, a chemical mechanical polishing slurry composition for polishing multilayer films was prepared in the same manner as Example 1, except that the pH value was adjusted to 4.5.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Example 5]:

In Example 1, a chemical composition for polishing multilayer films was prepared in the same manner as in Example 1, except that the pH value was adjusted to 4.5 and 0.005 weight percent of polyacrylic acid (PAA 1X) as a defect modifier was added. Mechanical polishing slurry composition.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Example 6]:

In Example 1, except that the pH value was adjusted to 4.5 and 0.005 weight percent of polyacrylic acid (PAA 5X) with a weight average molecular weight of 10,000 as a defect improver was added, a polyacrylic acid with a weight average molecular weight of 10,000 (PAA 5X) was prepared in the same manner as in Example 1. Chemical mechanical polishing slurry composition for polishing multi-layer films.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Example 7]:

In Example 1, except that the pH value was adjusted to 4.5 and 0.0025 weight percent of polyacrylic acid (PAA 5X) with a weight average molecular weight of 10,000 as a defect improver was added, a polyacrylic acid with a weight average molecular weight of 10,000 (PAA 5X) was prepared in the same manner as in Example 1. Chemical mechanical polishing slurry composition for polishing multi-layer films.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Comparative example 1]:

In Example 1, a chemical mechanical polishing slurry composition for polishing a multilayer film was prepared in the same manner as Example 1, except that polyacrylic acid (PAA 1X) as a defect improver was not added.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Comparative example 2]:

In Comparative Example 1, a chemical mechanical polishing slurry composition for polishing a multilayer film was prepared in the same manner as Comparative Example 1 except that the pH value was adjusted to 4.5.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Comparative example 3]:

In Example 1, a chemical mechanical polishing slurry composition for polishing multilayer films was prepared in the same manner as Example 1, except that the pH value was adjusted to 2.5.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Comparative Example 4]:

In Example 1, a chemical mechanical polishing slurry composition for polishing multilayer films was prepared in the same manner as Example 1, except that 0.15 weight percent polyacrylic acid (PAA 1X) was added.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Comparative example 5]:

In Example 1, a chemical mechanical polishing slurry composition for polishing multilayer films was prepared in the same manner as in Example 1, except that 0.001 weight percent of polyacrylic acid (PAA 5X) with a weight average molecular weight of 10,000 was added.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Comparative Example 6]:

In Example 1, a polyacrylic acid for polishing multilayer films was prepared in the same manner as in Example 1, except that the pH value was adjusted to 4.5 and 0.001 weight percent of polyacrylic acid (PAA 5X) with a weight average molecular weight of 10,000 was added. Chemical mechanical polishing slurry composition.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Comparative Example 7]:

In Example 1, except that the pH value was adjusted to 7.5 and 0.005 weight percent of polyacrylic acid (PAA 5X) with a weight average molecular weight of 10,000 was added, a polyacrylic acid for polishing multilayer films was prepared in the same manner as in Example 1. Chemical mechanical polishing slurry composition.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Comparative example 8]:

In Example 1, a chemical mechanical polishing slurry composition for polishing multilayer films was prepared in the same manner as Example 1, except that polystyrene sulfonic acid (PSSA) was added.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Comparative Example 9]:

In Example 1, chemical mechanical polishing for polishing multilayer films was prepared in the same manner as in Example 1, except that 2-acrylamide-2-methylpropanesulfonic acid (AMPS) was added as a defect improver. Slurry composition.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Comparative Example 10]:

In Example 1, a chemical mechanical polishing slurry composition for polishing a multilayer film was prepared in the same manner as Example 1, except that ammonium lauryl sulfate (ALS) was added as a defect improver.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

[Comparative Example 11]:

In Example 1, a chemical mechanical polishing slurry composition for polishing multilayer films was prepared in the same manner as Example 1, except that ammonium sulfate (APS) was added as a defect improver.

By using the prepared chemical mechanical polishing slurry composition for polishing multilayer films, polishing was performed under the same evaluation conditions as in Example 1.

The common polishing conditions of Examples 1 to 7 and Comparative Examples 1 to 11 are as follows:

[Polishing conditions]:

1. Polisher: NT (KCTECH)

2. Mat: IC 1000 (DOW company)

3. Carrier RPM: 78/83

4. Wafer pressure: 2psi

5. Flow rate: 250ml/min

6. Polishing time: 60 seconds

The measurement results of the defect occurrence rate based on the type, weight percentage, and pH of the polyacrylic acid contained in the chemical mechanical polishing slurry composition for polishing multilayer films of Examples 1 to 7 and Comparative Examples 1 to 7 are as shown in Table 1 below. Show.

Using KLA-Tencor's SP2XP equipment, the total number of defects before wafer evaluation (PRE) and the total number of defects after chemical mechanical polishing (POST) were measured in DSA mode, and calculated as the ratio of POST/PRE Defect incidence. [Table 1] pH defect improver defect Type weight percentage Post/Pre(%) Example 1 3.5 PAA 1X 0.025 3.504 Example 2 3.5 PAA 1X 0.005 7.472 Example 3 3.5 PAA 5X 0.005 6.988 Example 4 4.5 PAA 1X 0.025 7.156 Example 5 4.5 PAA 1X 0.005 9.864 Example 6 4.5 PAA 5X 0.005 7.806 Example 7 4.5 PAA 5X 0.0025 13.945 Comparative example 1 3.5 - - 36.68 Comparative example 2 4.5 - - 59.32 Comparative example 3 2.5 PAA 1X 0.025 37.685 Comparative example 4 3.5 PAA 1X 0.15 18.347 Comparative example 5 3.5 PAA 5X 0.001 19.674 Comparative example 6 4.5 PAA 5X 0.001 25.648 Comparative example 7 7.5 PAA 5X 0.005 37.891

Referring to Table 1, it was confirmed that the defect occurrence rates of Examples 1 to 7 including the defect improving agent were significantly lower than the defect occurrence rates of Comparative Examples 1 and 2 that did not include the defect improving agent.

In addition, from the comparison of the results of Comparative Examples 3 and 7 with the results of Examples 1 and 3, it can be confirmed that under the same conditions, when the pH value decreases (pH2.5) or increases (pH7.5) , the incidence of defects increases.

From the comparison of the results of Example 1 and the results of Comparative Example 4, it can be confirmed that under the same conditions, when the content of polyacrylic acid as a defect improving agent increases, the defect occurrence rate increases; from the results of Example 3 and Example 6 Comparing the results with the results of Comparative Examples 5 and 6, it was confirmed that under the same conditions, when the content of polyacrylic acid decreases, the defect occurrence rate increases.

The measurement results of the defect occurrence rate based on the type, weight percentage, and pH of the defect improving agent contained in the chemical mechanical polishing slurry composition for polishing multilayer films of Examples and Comparative Examples 8 to 11 are shown in Table 2 below.

Using KLA-Tencor's SP2XP equipment, the total number of defects before wafer evaluation (PRE) and the total number of defects after chemical mechanical polishing (POST) were measured in DSA mode, and calculated as the ratio of POST/PRE Defect incidence. [Table 2] pH defect improver defect Type weight percentage Post/Pre(%) Example 1 3.5 PAA 1X 0.025 3.504 Comparative example 8 3.5 PSSA 0.025 28.170 Comparative example 9 3.5 AMPS 0.05 26.204 Comparative example 10 3.5 ALS 0.025 27.169 Comparative example 11 3.5 APS 0.025 22.697

Referring to Table 2, it was confirmed that when another type of anionic surfactant was included as the defect improving agent instead of polyacrylic acid, a defect occurrence rate of more than 20% was measured.

In summary, the implementation has been described through limited examples, and those of ordinary skill in the art can make various modifications and variations to the above description. For example, the described technology is performed in a different order from the described method, and/or the described constituent elements are combined or combined in a different form from the described method, or are replaced by other constituent elements or equivalents, or Displacement can also achieve the same effect.

Therefore, other expressions, other embodiments, and equivalents within the scope of the claims all fall within the scope of the patent application.

Claims (13)

A chemical mechanical polishing slurry composition for polishing multi-layer films, which includes: polishing particles containing metal oxides in a colloidal state; surface roughness improvers, including water-soluble polymers; polishing conditioners, including organic acids; A polishing profile improver including a nonionic surfactant; and a defect improver in an amount of 0.0025 to 0.025 weight percent, the defect improver including an anionic surfactant including polyacrylic acid; The polishing particles are prepared by a liquid phase method and dispersed so that the surface of the polishing particles has a negative charge; the nonionic surfactant includes polyethylene glycol, polypropylene glycol, polyethylene-propylene copolymer, At least any one of the group consisting of polyalkyl oxide, polyoxyethylene, polyoxyethylene and polypropylene oxide; the weight average molecular weight of the nonionic surfactant is 100 to 1000; and the non-ionic surfactant is used for polishing multi-layer films The pH range of the chemical mechanical polishing slurry composition is 3.5 to 4.5. The chemical mechanical polishing slurry composition for polishing multi-layer films as described in item 1 of the patent application, wherein the anionic surfactant further includes polymethacrylic acid, polystyrene-acrylic acid copolymer, acrylic acid - At least any one of the group consisting of maleic acid copolymer, acrylic acid-ethylene copolymer, acrylic acid-acrylamide copolymer, and acrylic acid-polyacrylamide copolymer. The chemical mechanical polishing slurry composition for polishing multi-layer films as described in item 1 of the patent application, wherein the metal oxide includes polishing particles containing metal oxide coated with organic matter or inorganic matter, and the metal oxide includes At least any one selected from the group consisting of silicon dioxide, zirconium oxide, aluminum oxide, titanium dioxide, germanium oxide, manganese oxide and magnesium oxide. The chemical mechanical polishing slurry composition for polishing multi-layer films as described in item 1 of the patent application, wherein the particle size of the polishing particles is 10 nanometers to 200 nanometers. The chemical mechanical polishing slurry composition for polishing multi-layer films as described in item 1 of the patent application, wherein the polishing particles account for 0.1 to 10 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films. Weight percent. The chemical mechanical polishing slurry composition for polishing multi-layer films as described in item 1 of the patent application, wherein the weight average molecular weight of the water-soluble polymer is 10,000 to 1,000,000. The chemical mechanical polishing slurry composition for polishing multi-layer films as described in item 1 of the patent application, wherein the water-soluble polymer includes selected from the group consisting of hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl Cellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose, chitosan, gelatin, xanthan gum, collagen, carrageenan, pectin, sulfuric acid At least any one of the group consisting of chondroitin, alginic acid, dextran, β-glucan and hyaluronic acid. The chemical mechanical polishing slurry composition for polishing multi-layer films as described in item 1 of the patent application, wherein the surface roughness improver accounts for 0.0005 weight of the chemical mechanical polishing slurry composition for polishing multi-layer films. % to 0.5 weight percent. The chemical mechanical polishing slurry composition for polishing multi-layer films as described in item 1 of the patent application, wherein the organic acid includes succinic acid, malic acid, malonic acid, adipic acid, tartaric acid, pentanoic acid, Diacid, glycolic acid, aspartic acid, itaconic acid, malonic acid, pimelic acid, suberic acid, sebacic acid, stearic acid, pyruvic acid, acetoacetic acid, glyoxylic acid, azelaic acid , fumaric acid, glutaconic acid, traumatic acid, muconic acid, aconitic acid, tricarboxylic acid, tribasic acid, mellitic acid, isocitric acid, citric acid, lactic acid, gluconic acid, maleic acid, ascorbic acid, imine Acetic acid, oxalic acid, pyrogallic acid, formic acid, acetic acid, In the group consisting of propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, nonanoic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid and palmitic acid At least any of them. The chemical mechanical polishing slurry composition for polishing multi-layer films as described in item 1 of the patent application, wherein the polishing conditioner accounts for 0.01 to 0.01% by weight in the chemical mechanical polishing slurry composition for polishing multi-layer films. 1% by weight. The chemical mechanical polishing slurry composition for polishing multi-layer films as described in item 1 of the patent application scope also includes: a pH adjuster, the pH adjuster includes: triethanolamine, trimethanolamine, monoethanolamine , diethanolamine, dimethylbenzylamine, ethoxybenzylamine, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, tris(hydroxymethyl) )Aminomethane, 2-amino-1-butanol, 2-amino-2-methyl-1,3-propanediol, dimethylaminomethylpropanol, diethylaminoethanol, monoisopropanolamine, aminoethyl Ethylene ethanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 1-amino-pentanol, 2-(2-aminoethylamino)ethanol, 2 - At least one of the group consisting of dimethylamino-2-methyl-1-propanol and N,N-diethylethanolamine. The chemical mechanical polishing slurry composition for polishing multi-layer films as described in item 1 of the patent application, wherein the polishing profile improver accounts for 0.01 weight percent in the chemical mechanical polishing slurry composition for polishing multi-layer films. to 1 weight percent. The chemical mechanical polishing slurry composition for polishing multi-layer films as described in item 1 of the patent application, wherein the multi-layer film includes a polycrystalline silicon film, a silicon nitride film, or a combination of both.